Nowadays, volatile organic compound (VOC) detection is imperative to ensure environmental safety in industry and indoor environments, as well as to monitor human health in medical diagnosis. Gas sensors with the best sensor response, selectivity, and stability are in high demand. Simultaneously, the advancement of nanotechnology facilitates novel nanomaterial-based gas sensors with superior sensor characteristics and low power consumption. Recently, boron nitride, a 2D material, has emerged as an excellent candidate for gas sensing and demonstrated exceptional sensing characteristics for new-generation gas sensing devices. Herein, ultrathin porous boron nitride nanosheets (BNNSs) with large lateral sizes were synthesized using a facile synthesis approach, and their material characteristics were investigated utilizing a variety of analytical techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. A BNNS-coated cladding-modified fiber optic sensor (FOS) probe was prepared and employed for VOC (ammonia, ethanol, and acetone) sensing across concentrations varying from 0 to 300 ppm. The BNNSs-coated FOS demonstrated better selectivity toward 300 ppm ammonia, and specifically annealed BNNSs displayed a maximum sensor response of 55% along with a response/recovery times of 15 s/34 s compared to its counterparts. The superior ammonia sensing performances could be attributed to the formation of ultrathin nanosheets and a porous surface with slit-like features in hexagonal boron nitride.